Polymer-coated articles

ABSTRACT

Extended polymer compositions are provided which comprise polymers containing pendant functional groups of the formula: ##STR1## extended, i.e. admixed with a chalcogenide having the empirical formula ##STR2## wherein R 1  is a divalent organic radical at least 3 atoms in length, X is organoacyl or cyano, A is a chalcogen, each of R 9  and R 10  is independently selected from hydrogen, NR 11  R 12 , NR 13  and monovalent organic radicals, at least one of R 9  and R 10  being NR 11  R 12  or NR 13 , each of R 11  and R 12  is independently selected from hydrogen and monovalent organic radicals, and R 13  is a divalent organic radical. These compositions can be extended with significant proportions of the described chalcogenides with corresponding reductions in polymer concentration without significant loss of physical properties. The resulting combinations are particularly useful as binders and coatings.

This application is a division, of application Ser. No. 07/238,778,filed Aug. 31, 1988, now U.S. Pat. No. 5,055,510.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to the field of polymer compositions and, inparticular, it relates to adhesive and coating compositions,adhesive-bonded fiberous articles, e.g. textile and non-woven materials,and to methods for manufacturing such materials.

2. Introduction

The field of textile and non-woven materials involves all manufacturedforms of fiber assemblies including wovens, nonwovens, knitted articles,threads, yarns, ropes, bonded fiberous articles, such as mats, pads,diaper liners, all varieties of paper, tiles (e.g., acoustic tiles),etc. which are employed, in one form or another, in almost every aspectof commercial and household use, either alone or as components ofcomposite articles. (For ease of reference, the term "textile," as usedherein, includes bonded, non-woven, fiberous articles, such as papers,and fiberous mats, tiles and the like, as well as bonded woven andnon-woven fabrics.) All of these utilities place one or more similardemands on textile materials. Almost without exception, the textilematerial must have adequate tensile strength for its intended purpose,and such strength is often required under both wet and dry conditions.The most common "wet" conditions to which textiles are exposed occurduring manufacture, use, and cleaning and involve exposure to water,soap solutions, and/or dry cleaning solvents such as perchloroethylene.Textile materials exposed to flexing or tensile forces duringmanufacture, use, or cleaning require adequate flexibility, elongation(ability to stretch without breaking), and shape retention (ability toreturn to original dimensions after distortion). Since many textiles areexposed to wear during manufacture and use, they should possess adequateabrasion resistance, while those exposed to cleaning operations shouldhave adequate scrub, solvent, and detergent resistance. Many textiles,such as clothing articles, drapes, and various household and commercialtextiles, desirably have suitable "hand" (feel) for esthetic orutilitarian purposes Many textiles also must be sufficiently stable,both chemically and physically, to heat, light, detergents, solvents,and other conditions of exposure to prevent variations in physicalcharacteristics and/or discoloration, e.g. yellowing. Color stability,i.e., the retention of a textile's original color after exposure toheat, light, detergents, etc., is also desirable in many textilematerials, particularly in those requiring esthetic appeal.

While all of these properties are, to a large extent, dependent upon thechemical composition of the fibers employed and their mechanicalarrangement in the textile material, such properties can be, and oftenare, dependent upon the composition of chemicals, particularly polymericbinders, employed in their manufacture. Polymeric binders are widelyemployed to improve one or more physical properties of essentially allforms of textile materials. For instance, binders are used to improveshape retention, abrasion resistance, scrub resistance, and physical andchemical stability of woven and nonwoven textiles, knits, yarns, etc.The use of such binders to provide tensile strength as well as otherdesirable physical properties is a practical necessity in themanufacture of nonwoven textiles (also known as "formed" fabrics) whichare usually characterized as webs or mats of random or oriented fibersbonded together with a cementing medium, such as starch, glue, orsynthetic polymers. Synthetic polymers have largely displaced otherbonding agents in the manufacture of nonwovens and other textilematerials due primarily to improved physical properties they impart tothe finished textile.

Synthetic polymers are typically applied to textile materials assolutions or as dispersions of the polymer in an aqueous medium. Suchsolutions and dispersions must, of course, possess properties whichfacilitate their use in textile manufacture. For instance, the solutionor dispersion, as well as the polymer, must adequately wet the textilefibers to provide adequate distribution, coverage, and cohesiveness.Cohesiveness relates primarily to the ability of the polymer matrix toadhere to the textile fibers, particularly during manufacture and beforecuring has occurred. Rapid cure rate (the time required for the appliedpolymer to develop adequate strength in the textile material) is alsoimportant in manufacturing due to the demands of high speedmanufacturing facilities. While curing catalysts, such as oxalic acid,are employed to cure some polymers, such as polymers which containN-methylolamides, and they improve cure rate and physical properties, itis preferable, of course, to avoid the need for such catalysts. Thenecessity of catalyzing polymer curing increases cost and the technicalcomplexity of textile manufacture and can result in the presence ofundesirable toxic residues in the finished article.

The use of solvents other than water, while still widely practiced, isbecoming more and more undesirable due to solvent expense and the costsand hazards involved in controlling solvent vapors. Yet solvents arestill considered necessary to allow bonding of textile materials withpolymers which cannot be employed in water-base systems. Thus,water-base polymer latexes are much preferred in the textilemanufacturing industry, provided that the necessary physical andchemical properties can be achieved. However, substantial loss of one ormore physical properties often results upon substitution of water-baselatexes for solvent-base polymers. Latexes of polymers containingN-methylol-amide functional groups are known to improve physicalproperties in essentially all respects. However, such polymers releaseformaldehyde when cured, and they can result in formaldehyde residues inthe finished product. Formaldehyde is coming under ever-increasingscrutiny in both the workplace and home; it is particularly undesirablein medical applications, feminine hygiene products, diapers, and similararticles. To illustrate, Japanese Law No. 112 of 1973 sets a maximum of75 micrograms of formaldehyde per gram for all textiles used for anypurpose and zero (non-detectable) for infant wear products. Similar lawshave been proposed in the United States, and the state and federalOccupational Health and Safety Administrations (OSHA) have set stringentformaldehyde exposure limits for industrial workers. CaliforniaProposition 65 specifically identifies formaldehyde as a carcinogen andrequires that labels for all products containing any amount offormaldehyde, i.e. even on the parts per million level, contain acaution statement that the article is carcinogenic. Thus, paper towels,diapers, and any other articles containing even minuscule amounts offormaldehyde must be labeled as carcinogenic. The necessity for assuringthat formaldehyde is not present in manufactured articles is apparent.

Several rheological properties of water-base latexes are particularlyimportant with regard to their utility in the manufacture of textilematerials. For instance, control of latex particle size and particlesize distribution is critical to the realization of desirable physicalproperties in many polymer latexes. Another factor, latex viscosity, canlimit latex utility in textile manufacturing apparatus due to itsinfluence on polymer distribution, filler loading, and fiber wetting.

Thus, it can be seen that the physical and chemical properties requiredin textile materials, and in the polymer solutions and dispersionsemployed to manufacture such materials, place various, sometimesconflicting, demands on the polymer system employed. Obviously, it isdesirable to obtain a polymer system, preferably a water-base system,which possesses a wide range of properties desirable in the manufactureof textile materials.

Since cost of materials is always a factor in the production ofmanufactured articles, it is also desirable to provide polymer systemsand manufactured articles, such as textiles, that are as inexpensive aspossible, but which still possess the necessary physical and chemicalproperties. Obviously, cost can be reduced by employing less polymer inthe manufacture of articles, such as textiles, although this, almostinvariably, results in a loss of one or more desirable properties. Whileit is sometimes possible to extend polymer solutions, latexes or meltswith relatively inexpensive materials, that practice almost invariablyreduces one or more essential properties of the polymer system and ofarticles bonded with such polymers. The above-noted advantages ofemploying extended polymer compositions apply equally well to coatingand adhesive compositions, and it is desirable to extend all types ofcoating and adhesive compositions with materials less expensive than thepolymer itself with as little loss of desirable properties as ispossible.

SUMMARY OF THE INVENTION

It has now been found that extended polymer compositions, particularlyuseful as coatings and adhesives, which exhibit little or no loss ofdesirable physical properties can be obtained with polymers containingpendant functional groups of the formula: ##STR3## extended, i.e.admixed with a chalcogenide having the empirical formula: ##STR4##wherein A is a chalcogen, each of R₉ and R₁₀ is independently selectedfrom hydrogen, NR₁₁ R₁₂ or NR₁₃, at least one of R₉ and R₁₀ being otherthan hydrogen, each of R₁₁ and R₁₂ is independently selected fromhydrogen and monovalent organic radicals, and R₁₃ is a divalent organicradical. R₁ in formula (1) is a divalent organic radical at least 3atoms in length, and X is organoacyl or cyano.

These extended polymer compositions can be employed for all varieties cfcoatings and adhesives, including clear coating, paints, laminating andjoining adhesives or as primer coatings over which additional coatingsor materials are applied. They are particularly useful for bindingtextiles. Thus, they can be applied to fiber assemblies either assolutions or aqueous dispersions, although aqueous dispersions areparticularly preferred since they eliminate the costs and hazardsassociated with the use of polymer solvents. Such compositions can beemployed to improve the physical properties of essentially all forms oftextile materials including wovens, nonwovens, knits, threads, yarns,and ropes, and are particularly useful for the manufacture of nonwoven,knitted, and loose-weave materials. The polymers improve physicalproperties, including wet and dry tensile strength, of textile materialseven in the absence of monomers, such as the N-methylolamides, whichrelease formaldehyde upon curing. Nevertheless, the useful polymers maycontain minor amounts of such monomers. In addition to improving wet anddry tensile strength, these compositions result in textile materials ofimproved abrasion resistance, color stability, scrub resistance, andphysical stability (retention of physical strength) upon exposure toheat, light, detergent, and solvents. They have less tendency to yellowwith age than do polymers containing other monomers, such asN-methylolacrylamide, often employed to increase tensile strength. Thepolymers exhibit increased cohesion to fibers containing polar functiongroups prior to, during, and after cure, and the finished textilematerials have increased flexibility, elongation before break, and shaperetention at comparable polymer loadings. Yet these improvements are notachieved at a sacrifice of other desirable properties such asflexibility and "hand" which often results from the use of polymercompositions and/or concentrations capable of significantly increasingstrength and abrasion resistance. Thus, the finished textiles impart notonly improved properties in one or more respects, they exhibit animproved balance of desirable properties as well.

The same is true of the polymer solutions and latexes employed in thetextile manufacturing methods of this invention. Thus, latex viscosity,an important consideration in the manufacture of textile materials, islower than that of otherwise identical latexes of polymers which do notcontain the described functional monomers, and it is much less than thatof otherwise identical N-methylolacrylamide (NMOA)-containing polymers.Furthermore, latex viscosity is influenced less by latex particle sizeor particle size distribution. Also, latex particle size anddistribution have less, if any, effect on finished textile propertiesunder otherwise identical conditions. Hence, latexes of various particlesize and particle size distribution can be used in the samemanufacturing process for producing the same textile articles lessvariation in latex performance or product properties, and it is not asnecessary to control particle size or distribution from batch to batch.Since the latexes and solutions have lower viscosities (at similarsolids contents), they can be employed for the manufacture of textilearticles at higher filler and/or polymer concentrations withoutexceeding acceptable viscosity limits. Since curing catalysts andcross-linking agents, such as oxalic acid, multivalent complexing metalsor metal compounds, glycols, etc., are not required to achieve adequatebonding, such materials can be eliminated from these compositions withcommensurate reductions in expense and handling difficulties. Improvedfiber wetting, particularly by the useful water-based polymerdispersions, and increased cure rate further facilitate both the easeand speed of textile manufacture. The variety of beneficial propertiesexhibited by both the methods and textile articles of this inventionmakes possible the manufacture of a multiplicity of textile materialswith little or no reformulation of the useful polymer solutions ordispersions and thereby reduces the inventory of polymer materialsrequired for the manufacture of such various products.

The physical properties of the finished textile are influenced by latexpH to a much lesser extent than is the case with other polymer latexes,such as N-methylolamide-containing polymer latexes. Latexes ofN-methylolacrylamide-containing polymers produce maximum textile tensilestrengths when applied to textile substrates at a pH of about 2, andfinished article tensile strength decreases as pH is increased. Thisbehavior of NMOA-containing polymers greatly limits the pH range withinwhich they can be applied to textile fibers and results in the exposureof manufacturing and handling equipment to acidic corrosive latexes. Incontrast, the finished tensile strengths obtained with the latexesuseful in this invention changes much less with pH, generally increasesas pH is increased from about 2 to about 7, and is typically maximum ata pH within the range of about 4 to about 8. Furthermore, the variationin final product tensile strength over the full pH range, i.e., fromaround 0.5 to 12, is much less significant than that observed withNMOA-containing polymers. Thus, the methods of this invention can bepracticed over a much broader pH range without significant sacrifice ofproduct tensile strength. For the same reason, these methods can beemployed to treat acid-sensitive materials and can containacid-sensitive components which might otherwise be degraded by exposureto acidic latexes.

The presence of the described chalcogenides provides yet furtheradvantages, in that the chalcogenides reduce the amount of relativelyexpensive polymer that must be present in the composition, yet do notsignificantly impair, and sometimes even improve, the desired physicalproperties of the polymer composition. Thus, the desirable processing,coating and binding properties of the compositions can be achieved withmuch lower polymer concentrations than would be necessary in the absenceof the described chalcogenides. In addition, polymer compositionsextended with the described chalcogenides also exhibit superior coatingand binding properties when employed to bind materials other thantextiles. Thus, these compositions can be employed to bind two or moresurfaces together and to produce laminates of or coatings on a varietyof substrates, such as plastics, wood and other cellulosic materialssuch as cardboard, paper and the like.

DETAILED DESCRIPTION

Extended polymer compositions exhibiting little or no significant lossof desirable physical properties due to the presence of the extender,particularly useful as coatings and adhesives, are provided whichcomprise the polymer hereinafter defined extended with one or more ofthe hereinafter-described chalcogenides. In one embodiment, textilematerials having improved physical properties are provided, whichmaterials comprise fiber assemblies containing a polymer havingpolymerized, olefinically unsaturated carboxylic acid ester groups andpendant functional groups of the formula: ##STR5## wherein R₁ is adivalent organic radical at least 3 atoms in length, and X is organoacylor cyano. Thus, X is --CO--R₄ or --CN, preferably --CO--R₄, where R₄ ishydrogen or a monovalent organic radical preferably having up to about10 atoms other than hydrogen (i.e., up to 10 atoms not counting hydrogenatoms which may be present in the radical).

Functional groups containing different R₁ and X radicals can becontained in the same polymer molecule, or polymers containing differentR₁ and X groups can be blended in the same solution or dispersion. It isessential only that the useful polymers contain functional groupscontaining either two carbonyl groups or a carbonyl and a cyano groupseparated by a single methylene group, as illustrated, and the methylenegroup is separated from the polymer main chain (backbone) by at least 4atoms (R₁ plus the "interior" carbonyl group). Thus, R is at least 3atoms in length; i.e., the shortest link between the interior carbonylgroup and the polymer backbone is at least 3 atoms long. Otherwise, themolecular weight, structure and elementary composition of R₁ does notnegate the effectiveness of the dual keto or keto-cyano functionality ofthe pendant side chains Thus, R₁ can be of any molecular weightsufficient to allow incorporation of the pendant functional groups intothe polymer backbone, for instance, as part of a polymerizableolefinically unsaturated monomer or by substitution onto a preferredpolymer by any suitable addition reaction, e.g.: ##STR6## where n is aninteger, and --O--R₂ is R₁ in expression (1), supra. R₁ can containheteroatoms, such as oxygen, sulfur, phosphorus, and nitrogen,functional groups such as carbonyls, carboxy-esters, thio, and aminosubstituents, and can comprise aromatic, olefinic or alkynylunsaturation. Typically, R₁ will be a cyclic or acyclic divalent organicradical of 3 to about 40 atoms in length; i.e., having 3 to about 40atoms in its shortest chain between the polymer backbone and theinterior carbonyl group. For ease of manufacture from readily availablereactants, R₁ is preferably of the formula: ##STR7## wherein Y and Z areindependently selected from O, S, and NR₇, and R₃ is a divalent organicradical at least 1 atom in length, preferably 2 to about 40 and mostpreferably 2 to about 20 atoms in length. Y and Z are preferably O, andR₇ is H or a monovalent organic radical, preferably H or hydrocarbylradical having up to 6 carbon atoms, with R₇ most preferably being H.

Most preferably, R₃ is selected from substituted or unsubstitutedalkylene, polyoxyalkylene, polythythioalkylene and polyaminoalkylene upto about 40 atoms in length, preferably up to about 20 atoms in length.The substituted and unsubstituted polythio-, polyoxy-, andpolyamonioalkylenes can be readily formed by the well known condensationof alkylene oxides, alkylene amines, glycols, diamines, and dithiols.Thus: ##STR8## where R₈ is H or a monovalent organic radical, preferablyH or alkyl radical. To illustrate, such pendant functional groups(formula 1) can be introduced into the polymer backbone bycopolymerization of other monomers (discussed hereinafter) with apolymerizable monomer of the formula: ##STR9## wherein X is as definedfor formula 1, supra, R₆ and R₅ are independently selected from hydroxy,halo, thio, amino, and monovalent organic radicals, preferably having upto 10 atoms other than hydrogen, most preferably alkyl radicals havingup to 10 carbons atoms. Substituting the preferred form of the group R₁illustrated in formula 2 for R₁ in formula 1 yields the most preferredfunctional monomers: ##STR10## where R₃, R₅, R₆, X, Y and Z have thedefinitions given above. From this expression it can be seen that whenR₆ is hydrogen, X is --CO--R₄, R₄ and R₅ are methyl, Y and Z are O, andR₃ is an ethylene radical, the resulting monomer isacetoacetoxyethylmethacrylate, one of the class of monomers described bySmith in U.S. Pat. No. 3,554,987, the disclosure of which isincorporated herein by reference in its entirety. This monomer can beprepared by first treating ethylene glycol with methyacrylic acid toform hydroxyethyl methacrylate which is then treated with diketene, asdescribed by Smith, to form acetoacetoxyethylmethacrylate. Aparticularly preferred class of functional monomers, due to theirrelative availability, are those disclosed by Smith, which correspond toformula (4) in which R₆ is hydrogen, Y and Z are oxygen, R₅ is hydrogenor an alkyl group having up to 12 carbon atoms, R₃ is an alkylene groupcontaining up to 10 carbon atoms, X is --CO--R₄ and R₄ is an alkyl grouphaving up to 8 carbon atoms.

Regarding the following, above-described radicals, typically R₁ and R₃each contain no more than 40 carbon atoms, and R₄, R₅, R₆ and R₇ eachcontain no more than 20 carbon atoms. More typically, R₁ and R₃ eachcontain no more than 20 carbon atoms, R₄, R₅, and R₆ each contain nomore than 10 carbon atoms, and R contains no more than 6 carbon atoms.

As used herein, the term "organic radical" refers to any groupcontaining at least one carbon atom. Included therefore are aliphaticand aromatic radicals, whether containing only hydrogen and carbon(i.e., hydrocarbon radicals) or further containing heteroatoms such asoxygen, phosphorus, sulfur, and nitrogen and/or an inorganicsubstitutent such as chlorine, bromine, iodine, etc. Accordingly, suchradials include, for example, substituted and unsubstituted alkyl, aryl,arylalkyl, alkylaryl, alkyloxy, aryloxy, arylalkyloxy, alkenyl,alkenyloxy, alkynl, alkynyloxy, and arylalkenyl radicals andheteroatom-containing hydrocarbyl radicals wherein the heteroatoms arepreferably selected from oxygen, phosphorus, sulfur, and nitrogen atoms.

Any polymer containing at least one pendant functional group of formula(1), supra, can be employed as the polymer in this invention. Theremainder of the polymer, i.e., the portion of the polymer other thanthe pendant functional groups of formula (1), may be any polymerizedolefinically unsaturated monomer or mixture of such monomers, it beingessential only that the polymer contain the above-defined functionalmonomers. Illustrative of other polymerized monomers which can make upthe remainder of the polymer are, for example, (A) conjugated diolefinpolymers comprising, e.g. about 50 weight percent of one or moreconjugated diene monomers having 5 to about 8 carbon atoms and 0 toabout 50 weight percent of one or more alkenyl-substituted monoaromaticmonomers, (B) olefin-ester interpolymers comprising, e.g. about 1 weightpercent or more of a monoolefin monomer having up to about 4 carbonatoms and about 40 weight percent or more of an alkenyl or alkenol esterof a saturated carboxylic acid, (C) olefinically unsaturated carboxylicacid ester polymers comprising, e.g. about 40 weight percent or morepolymerized olefinically unsaturated carboxylic acid ester monomers, (D)alkenyl ether polymers containing, e.g. about 30 weight percent or morealkenyl ether monomer units, (E) polymers of vinylidene chloride orvinyl chloride with or without other comonomers such as olefinicallyunsaturated carboxylic acid ester monomers and/or olefinicallyunsaturated carboxylic acid monomers and (F) combinations thereof. Thepolymers of group (C) are presently preferred, i.e., the remainder ofthe polymer containing at least one pendant functional group of formula(1) preferably comprises at least about 40 weight percent of at leastone polymerized olefinically unsaturated carboxylic acid ester monomer.

The polymers contain a sufficient amount of one or more of the describedfunctional monomers to improve one or more physical properties of thecoating or adhesive composition relative to a similar coating oradhesive composition containing a similar polymer absent such functionalmonomers. Generally, these polymers will contain at least about 0.5,often at least about 1 weight percent of the functional monomer based ontotal monomer content. Increasing the concentration of the describedfunctional monomers to a level substantially above 20 weight percentgenerally does not produce significantly greater technical effects.Thus, functional monomer concentrations will usually be between about0.5 to about 20 weight percent, typically about 0.5 to about 10 weightpercent. Significant improvements in the physical properties describedabove usually can be achieved at functional monomer concentrations ofabout 0.5 to about 10 weight percent.

The useful functional monomers produce significant improvements incoating and bonding properties when employed with polymers which containsignificant amounts of polymerized, olefinically unsaturated mono-and/or polycarboxylic acid esters. Thus, the polymers will usuallycontain at least about 10 weight percent, often at least about 20 weightpercent, and preferably at least about 30 weight percent of olefinicallyunsaturated, carboxylic acid ester monomers other than theabove-described functional monomers. The most preferred polymers containat least about 50 weight percent, generally at least about 80 weightpercent, of such ester monomers. Presently preferred ester monomers areesters of olefinically unsaturated mono- or dicarboxylic acids having upto 10 carbon atoms, and hydroxy-, amino-, or thio-substituted orunsubstituted alcohols, amines, and thiols having from 1 to about 30carbon atoms, preferably 1 to about 20 carbon atoms, per molecule.Illustrative unsaturated carboxylic acids are acrylic, methacrylic,fumaric, maleic, itaconic, etc. Illustrative hydroxy-, amino-, andthio-substituted alcohols, amines, and thiols are glycerol,1-hydroxy-5-thiododecane, 2-amino-5-hydroxyhexane, etc. Presentlypreferred esters, due primarily to cost and availability, are acrylicand methacrylic acid esters of hydroxy-substituted and unsubstitutedalcohols, in which the alcohol moiety has up to about 10 carbon atoms,such as butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate,2-hydroxyethyl acrylate, etc.

The described functional monomers and ester monomers can constitute thetotal polymer composition, or the portion of the polymer molecule notaccounted for by those two monomer classes can be any polymerizable,olefinically unsaturated monomer or combination of monomers.Illustrative of such other polymerizable monomers are vinyl esters ofcarboxylic acids, the acid moiety of which contains from 1 to about 20carbon atoms (e.g., vinyl acetate, vinyl propionate, vinyl isononoate);aromatic or aliphatic, alpha-beta-unsaturated hydrocarbons such asethylene, propylene, styrene, and vinyl toluene; vinyl halides such asvinyl chloride and vinylidene chloride; olefinically unsaturatednitriles such as acrylonitrile; and olefinically unsaturated carboxylicacids having up to 10 carbon atoms such as acrylic, methacrylic,crotonic, itaconic, and fumaric acids, and the like. It has been foundthat minor amounts of olefinically unsaturated carboxylic acids, acidamides, acid nitriles and/or sulfoalkyl esters of such carboxylic acidssignificantly improve tensile strength and/or other physical propertiesof the finished textile material. Thus, it is presently preferred thatthe polymer contain at least about 0.1 weight percent, usually about 0.1to about 10 weight percent, and preferably about 0.1 to about 5 weightpercent of a polymerizable, olefinically unsaturated carboxylic acid,acid amide and/or acid nitrile having up to about 10 carbon atoms and/ora sulfoalkyl ester of such acids, such as acrylic acid, itaconic acid,acrylamide, methacrylamide, acrylonitrile, sulfoethyl methacrylate,sulfoethyl itaconate, sulfomethyl maleate, etc.

Although the polymers can contain other functional monomers, such asN-methylolamides, e.g., N-methylolacrylamide (NMOA), it has been foundthat such other functional monomers are not essential to achievingacceptable physical properties in bonded or coated articles and that thedetriment associated with the presence of such monomers, such asformaldehyde release upon curing, can be avoided by minimizing theconcentration of such N-methylolamides, or eliminating them altogether.Thus, the preferred polymers contain less than about 1 percent,preferably less than about 0.5 percent, and most preferably no amount ofN-methylolamide monomer units.

It has also been found that suitable physical properties of bonded orcoated articles can be achieved without the need of cross-linking orhardening agents such as aldehyde hardeners (e.g., formaldehyde,mucochloric acid, etc.), cross-linking catalysts such as the strong basecatalysts discussed by Bartman in U.S. Pat. No. 4,408,018, or acidcatalysts such as phosphoric or methane sulfonic acid, complexing agentssuch as metals and metal compounds, or reactive monomers (e.g., glycols,polyamides, etc.). Since, to some extent, addition of such "hardening"agents increases the complexity and expense of polymer and/or textilemanufacture, and since such agents are not required to achieve thedesired physical properties with the polymers of this invention, thepreferred polymers and finished articles are preferably substantiallyfree of such hardening agents or their residues. Nevertheless, minoramounts of such materials can be present in the useful polymer solutionsor dispersions when their presence does not detrimentally affectdesirable properties of the finished article and when the beneficialeffect of such materials can be justified economically.

Aqueous dispersions and solvent-containing solutions of the usefulpolymers can be prepared by procedures known in the art to be suitablefor the preparation of olefinically unsaturated carboxylic acid esterpolymers, such as acrylic ester polymers. For instance, aqueous polymerdispersions can be prepared by gradually adding each monomersimultaneously to an aqueous reaction medium at rates proportionate tothe respective percentage of each monomer in the finished polymer andinitiating and continuing polymerization by providing in the aqueousreaction medium a suitable polymerization catalyst. Illustrative of suchcatalysts are free radical initiators and redox systems such as hydrogenperoxide, potassium or ammonium peroxydisulfate, dibenzoyl peroxide,lauryl peroxide, di-tertiarybutyl peroxide, bisazodiisobutyronitrile,either alone or together with one or more reducing components such assodium bisulfite, sodium metabisulfite, glucose, ascorbic acid,erythorbic acid, etc. The reaction is continued with agitation at atemperature sufficient to maintain an adequate reaction rate until alladded monomers are consumed. Monomer addition is usually continued untilthe latex (dispersion) reaches a polymer concentration of about 10 toabout 60 weight percent.

Physical stability of the dispersion is achieved by providing in theaqueous reaction medium, one or more surfactants (emulsifiers) such asnon-ionic, anionic, and/or amphoteric surfactants. Illustrative ofnon-ionic surfactants are alkylpolyglycol ethers such as ethoxylationproducts of lauryl, oleyl, and stearyl alcohols or mixtures of suchalcohols such as coconut fatty alcohol; alkylphenol polyglycol etherssuch as ethoxylation products of octyl- or nonylphenol,diisopropyl-phenol, triisopropyl-phenol, di- or tritertiarybutylphenol,etc. Illustrative of anionic surfactants are alkali metal or ammoniumsalts of alkyl, aryl, or alkylaryl sulfonates, sulfates, phosphates,phosphonates, etc. Illustrative examples include sodium lauryl sulfate,sodium octylphenol glycolether sulfate, sodium dodecylbenzene sulfonate,sodium lauryldiglycol sulfate, and ammonium tritertiarybutylphenol,penta- and octa-glycol sulfates. Numerous other examples of suitableionic, nonionic and amphoteric surfactants are disclosed in U.S. Pat.Nos. 2,600,831, 2,271,622, 2,271,623, 2,275,727, 2,787,604, 2,816,920,and 2,739,891, the disclosures of which are incorporated herein byreference in their entireties.

Protective colloids may be added to the aqueous polymer dispersioneither during or after the reaction period. Illustrative protectivecolloids include gum arabic, starch, alginates, and modified naturalsubstances such as methyl-, ethyl-, hydroxyalkyl-, and carboxymethylcellulose, and synthetic substances such as polyvinyl alcohol, polyvinylpyrrolidone, and mixtures of two or more of such substances. Fillersand/or extenders, in addition to the described chalcogenides, such asdispersible clays and colorants, including pigments and dyes, can alsobe added to the aqueous dispersions either during or afterpolymerization.

One additional advantage of the polymers useful in this invention isthat their solutions and dispersions, and particularly their dispersionsin aqueous media, are of lower viscosity than are ester polymers notcontaining the functional monomers useful in this invention, and theyhave much lower viscosities than N-methylolamide-containing polymerdispersions. Thus, the latexes have viscosities of about 100 centipoiseor less, often about 50 centipoise or less measured at 21° C. at polymerconcentration of 40 weight percent or more and even of 50 weight percentand more. Polymer concentrations of about 40 to about 70 percentencompass most latexes resulting from emulsion polymerization, whilepreferred latexes typically have solids contents of about 40 to about 60weight percent polymer solids. The observed low viscosity behavior ofthe concentrated latexes is atypical, particularly for polymers havingcomparable molecular weights and for latexes of comparable particlesize. These polymers usually have number average molecular weights of atleast about 40,000 and most often at least about 50,000. Typically,polymer molecular weight maximums are about 150,000 or less, generallyabout 100,000 or less. The dispersed polymer particles in the latex canbe of any size suitable for the intended use although particle sizes ofat least about 120 nanometers are presently preferred since latexviscosity increases as particle size is reduced substantially below thatlevel. Most often, the described latexes will have polymer particlesizes within the range of about 120 to about 300 nanometers asdetermined on the N-4 "Nanosizer" available from Coulter Electronics,Inc., of Hialeah, Fla. Accordingly, the polymer content of both theaqueous dispersions and solutions can be increased or the loading of thedispersions and solutions with fillers such as clays, pigments, andother extenders can be increased without exceeding permissible viscositylimits. For instance, aqueous dispersions and polymer solutions cancontain more than 2 percent, often more than 5 percent, and even morethan 10 percent fillers, colorants and/or extenders, in addition to thedescribed chalcogenides.

Solutions of the useful polymers can be prepared by polymerizing theselected monomers as described above in solvents in which both themonomers and the polymers are soluble. Suitable solvents includearomatic solvents such as xylene and toluene and alcohols such asbutanol. Polymerization initiators and reducing components, whenemployed, should be soluble in the selected solvent or mixture ofsolvents. Illustrative polymerization initiators soluble in the notedorganic solvents include dibenzoyl peroxide, lauryl peroxide, andbisazodiisobutyronitrile. Erythorbic and ascorbic acids are illustrativeof reducing components soluble in polar organic solvents.

The extended polymer compositions comprise one or more of theabove-described polymers, polymer solutions or latexes in combinationwith a chalcogenide of the formula ##STR11## wherein A is a chalcogen,R₉ and R₁₀ are independently chosen from hydrogen, NR₁₁ R₁₂, NR₁₃, ormonovalent organic radicals, with at least one of R₉ and R₁₀ being NR₁₁R₁₂ or NR₁₃, R₁₁ and R₁₂ are independently chosen from hydrogen andmonovalent organic radicals, and R is a divalent organic radical. Eitheror both of R₁₁ and R₁₂, and one of R₉ and R₁₀, can be any monovalentorganic radical, typically having 1 to about 10, preferably 1 to about 5atoms other than hydrogen, including, for example, alkyl, aryl, alkenyl,alkenylaryl, aralkyl, aralkenyl, cycloakyl, cycloalkenyl, or akynyl,which can be unsubstituted or substituted with pendant functional groupssuch as hydroxyl, carboxyl, oxide, thio, thiol, or others, and they cancontain acyclic or cyclic heteroatoms such as oxygen, sulfur, nitrogen,phosphorus, or others. R₁₃ can be any divalent organic radical such asalkdyl, ardyl, alkenydyl, alkyndyl, aralkdyl, aralkendyl, which maycontain pendant atoms or substituents and/or acyclic or cyclicheteroatoms as described for R₁₁ and R₁₂. Preferably, both R₉ and R₁₀are NR₁₁ R₁₂ or NR₁₃, both R₁₁ and R₁₂ are selected from hydrogen andorganic radicals which contain about 10 atoms other than hydrogen orless, R₁₃ is a divalent organic radical having 10 atoms or less otherthan hydrogen, and Y is preferably oxygen or sulfur. Most preferably, R₉and R₁₀ are hydrogen or NR₁₁ R₁₂, where R₁₁ and R₁₂ are independentlyselected from saturated organic radicals having 10 atoms or less otherthan hydrogen which can contain pendant substituents and heteroatoms asdescribed above. When the described polymer-chalcogenide combinationsare to be manufactured and/or used in aqueous media, i.e., as a polymerlatex, the chalcogenides are preferably water-dispersible, and mostpreferably they are water soluble. Particularly preferred chalcogenidesare urea, thiourea, formamide, polymers of urea and thiourea, such asbiuret, triuret and the sulfur analogues thereof, mono- and dialkylsubstituted ureas, thioureas, polymeric ureas and thioureas, formamidesand thioformamides, with the alkyl groups having 10 carbon atoms orless, preferably 5 carbon atoms or less, and combinations of these. Thechalcogens are elements of Periodic Group VI-B and include oxygen,sulfur, selenium, tellurium, and polonium. Oxygen and sulfur arepresently preferred due to low cost, availability, low toxicity andchemical activity.

The described chalcogenides can be combined with the described polymersby admixing the solid chalcogenide, or a solution thereof in water orother solvent, with the polymer latex or solution, or the polymer can beformed in the presence of the chalcogenide by adding the latter to themonomer emulsion (in the case of latexes) or solution (in the case ofsolution polymers) before or during polymerization. Preferably, however,the chalcogenide is combined with the polymer after polymerization iscomplete, and addition of the chalcogenide can even be deferred untilshortly before use of the composition as an adhesive. Thus, the polymercan be manufactured at one site as a latex or solution, shipped to theuser's site, and there admixed with the chalcogenide as described above.

While minor amounts of chalcogenide can be employed to extend thepolymer compositions, the most significant improvements in economy,without intolerable reductions in adhesive properties, are realized atchalcogenide concentrations sufficient to significantly reduce theamount of polymer required. Thus, one or more of the describedchalcogenides are combined with the polymer in any proportion, usuallyat concentrations of at least about 5, generally at least about 10,preferably at least about 20, and most preferably, at least about 30weight percent based on the combined weight of chalcogenide and drypolymer.

As illustrated by the examples discussed hereinafter, relatively highchalcogenide concentrations can be employed without intolerable loss ofphysical properties. In most cases, physical properties do not begin todiminish significantly until chalcogenide concentrations in excess of 50weight percent, based on dry polymer, although higher concentrations canbe employed when slight reductions in adhesive and/or coating propertiescan be tolerated. Thus, chalcogenide concentrations will usually beabout 70 weight percent or less, most often about 50 weight percent orless based on dry polymer. Accordingly, chalcogenide concentrations willusually be within the range of about 5 to about 70, preferably about 10to about 50 weight percent based on chalcogenide plus dry polymer.

Without intending to be constrained to any particular theory, it ispresently believed that the described chalcogenides can be employed tosignificantly extend the polymer compositions without intolerable lossof binding or coating properties, since they appear to form bonds orenhance bonding between the described polymers and polar groups on thebound substrate upon curing of the polymer composition. This explanationis supported by carbon nuclear magnetic resonance analyses which showthat, upon curing, the resonance line of the pendant functional groupcarbonyl diminishes or disappears when reacted with a chalcogen and isreplaced by an amide-like structure indicating that bonding of some typeoccurs between the chalcogenide and carbonyl groups of the pendantfunctional groups described above. That mechanism may also facilitatebonding the polymer to the substrate, which is also supported by theresults of the examples discussed hereinafter illustrating that thechalcogenides can be substituted for a large proportion of polymerwithout significant loss of binder or coating properties.

Textile substrates useful in the textile articles of this inventioninclude assemblies of fibers, preferably fibers which contain polarfunctional groups. Significantly greater improvements in tensilestrength and other physical properties are achieved by application ofthe useful polymers to natural or synthetic polar group-containingfibers in contrast to relatively nonpolar fibers such as untreated,nonpolar polyolefin fibers. However, such nonpolar fibers also can beemployed. Furthermore, polar groups, such as carbonyl (e.g., keto) andhydroxy groups, can be introduced into polyolefins, styrene-butadienepolymers and other relatively nonpolar fibers by known oxidationtechniques, and it is intended that such treated polymers can beemployed in the articles and methods of this invention.

For the purposes of this invention, it is intended that the term"fibers" encompass relatively short filaments or fibers as well aslonger fibers often referred to as "filaments." Illustrative polarfunctional groups contained in suitable fibers are hydroxy, etheral,carbonyl, carboxylic acid (including carboxylic acid salts), carboxylicacid esters (including thio esters), amides, amines etc. Essentially allnatural fibers include one or more polar functional groups. Illustrativeare virgin and reclaimed cellulosic fibers such as cotton, wood fiber,coconut fiber, jute, hemp, etc., and protenaceous materials such as wooland other animal fur. Illustrative synthetic fibers containing polarfunctional groups are polyesters, polyamides, carboxylatedstyrene-butadiene polymers, etc. Illustrative polyamides includenylon-6, nylon-66, nylon-610, etc.; illustrative polyesters include"Dacron," "Fortrel," and "Kodel"; illustrative acrylic fibers include"Acrilan," "Orlon," and "Creslan." Illustrative modacrylic fibersinclude "Verel" and "Dynel." Illustrative of other useful fibers whichare also polar are synthetic carbon, silicon, and magnesium silicate(e.g., asbestos) polymer fibers and metallic fibers such as aluminum,gold, and iron fibers.

These and other fibers containing polar functional groups are widelyemployed for the manufacture of a vast variety of textile materialsincluding wovens, nonwovens, knits, threads, yarns, and ropes. Thephysical properties of such articles, in particular tensile strength,abrasion resistance, scrub resistance, and/or shape retention, can beincreased by addition of the useful polymers with little or nodegradation of other desirable properties such as hand, flexibility,elongation, and physical and color stability.

The useful polymers can be applied to the selected textile material byany one of the procedures employed to apply other polymeric materials tosuch textiles. Thus, the textile can be immersed in the polymer solutionor dispersion in a typical dip-tank operation, sprayed with the polymersolution or dispersion, or contacted with rollers or textile "printing"apparatus employed to apply polymeric dispersions and solutions totextile substrates. Polymer concentration in the applied solution ordispersion can vary considerably depending primarily upon theapplication apparatus and procedures employed and desired total polymerloading (polymer content of finished textile). Thus, polymerconcentration can vary from as low as about 1 percent to as high as 60percent or more, although most applications involve solutions ordispersions containing about 5 to about 60 weight percent latex solids.

Textile fiber assemblies wetted with substantial quantities of polymersolutions or latexes are typically squeezed with pad roll, knip roll,and/or doctor blade assemblies to remove excess solution or dispersionand, in some instances, to "break" and coalesce the latex and improvepolymer dispersion and distribution and polymer-fiber wetting. Thepolymer-containing fiber assembly can then be allowed to cure at ambienttemperature by evaporation of solvent or water although curing istypically accelerated by exposure of the polymer-containing fiberassembly to somewhat elevated temperatures such as 90° C. to 200° C. Oneparticular advantage of the useful polymers is that they cure relativelyfast. Thus, bond strength between the polymer and fibers, and thus,between respective fibers, develops quickly. Rapid cure rate isimportant in essentially all methods of applying polymers to textilessince it is generally desirable to rapidly reduce surface tackiness andincrease fiber-to-fiber bond strength. This is particularly true in themanufacture of loose woven textiles, knits, and nonwovens including allvarieties of paper. Most often, adequate bond strength and sufficientlylow surface tackiness must be achieved in such textiles before they canbe subjected to any significant stresses and/or subsequent processing.While cure rate can be increased with more severe curing conditions,i.e., using higher temperatures, such procedures require additionalequipment, increased operating costs, and are often unacceptable due toadverse effects of elevated temperatures on the finished textile.

The polymer content of the finished textile can vary greatly dependingon the extent of improvement in physical properties desired. Forinstance, very minor amounts of the useful polymers are sufficient toincrease tensile strength, shape retention, abrasion resistance (wearresistance), and/or wet-scrub resistance of the textile fiber assembly.Thus, polymer concentrations of at least about 0.1 weight percent,generally at least about 0.2 weight percent, are sufficient to obtaindetectable physical property improvements in many textiles. However,most applications involve polymer concentrations of at least about 1weight percent and preferably at least about 2 weight percent based onthe dry weight of the finished polymer-containing textile article.Polymer concentrations of about 1 to about 95 weight percent can beemployed, while concentrations of about 1 to about 30 weight percentbased on finished textile dry weight are most common.

The product property in which the most significant improvement resultsdepends, at least to some extent, on the structure of the treated fiberassemblage. For instance, threads and ropes formed from relatively long,tightly wound or interlaced fibers and tightly woven textiles generallypossess significant tensile strength in their native state, and thepercentage increase in tensile strength resulting from polymer treatmentwill be less, on a relative basis, than it is with other products suchas loose-wovens, knits, and non-wovens. More specifically, significantimprovements in abrasion resistance and scrub resistance are achieved inthreads, ropes, and tightly woven textiles, and significant improvementin tensile strength (both wet and dry) can be realized in such productswhich are manufactured from relatively short fibers and which thus havea relatively lower tensile strength in their native form. Usually themost significant improvements sought in loose-woven textiles are shaperetention (including retention of the relative spacing of adjacent wovenstrands), abrasion resistance, and scrub resistance, and theseimprovements can be achieved by the methods and with the articles ofthis invention. Similar improvements are also obtained in knittedfabrics.

The most significant advantages of the useful methods and textilearticles are in the field of non-wovens. Non-wovens depend primarily onthe strength and persistence of the fiber-polymer bond for theirphysical properties and for the retention of such properties with use.Bonded non-woven fabrics, such as the textile articles of thisinvention, can be defined generally as assemblies of fibers heldtogether in a random or oriented web or mat by a bonding agent. Whilemany non-woven materials are manufactured from crimped fibers havinglengths of about 0.5 to about 5 inches, shorter or longer fibers can beemployed. The utilities for such non-wovens range from hospital sheets,gowns, masks, and bandages to roadbed underlayment supports, diapers,roofing materials, napkins, coated fabrics, papers of all varieties,tile backings (for ungrouted tile prior to installation), and variousother utilities too numerous for detailed listing. Their physicalproperties range all the way from stiff, board-like homogeneous andcomposite paper products to soft drapeable textiles (e.g., drapes andclothing), and wipes. The myriad variety of non-woven products can begenerally divided into categories characterized as "flat goods" and"highloft" goods, and each category includes both disposable and durableproducts. Presently, the major end uses of disposable flat goodsnon-wovens include diaper cover stock, surgical drapes, gowns, facemasks, bandages, industrial work clothes, and consumer and industrialwipes and towels such as paper towels, and feminine hygiene products.Current major uses of durable flat goods non-wovens include apparelinterlinings and interfacings, drapery and carpet backings, automotivecomponents (such as components of composite landau automobile tops),carpet and rug backings, and construction materials, such as roadbedunderlayments employed to retain packed aggregate, and components ofcomposite roofing materials, insulation, pliable or flexible siding andinterior wall and ceiling finishes, etc.

The so-called "highloft" non-wovens can be defined broadly as bonded,non-woven fibrous structures of varying bulks that provide varyingdegrees of resiliency, physical integrity, and durability depending onend use. Currently, major uses of highloft non-wovens include themanufacture of quilts, mattress pads, mattress covers, sleeping bags,furniture underlayments (padding), air filters, carpet underlayments(e.g., carpet pads), winter clothing, shoulder and bra pads, automotive,home, and industrial insulation and paddings, padding and packaging forstored and shipped materials and otherwise hard surfaces (e.g.,automobile roof tops, chairs, etc.), floor care pads for cleaning,polishing, buffing, and stripping, house robes (terrycloth, etc.), cribkick pads, furniture and toss pillows, molded packages, and kitchen andindustrial scrub pads.

The polymers and methods can be used to manufacture all such non-wovens,and they are particularly useful for the manufacture of non-wovens freeof, or having reduced levels of, formaldehyde or other potentially toxiccomponents and which have relatively high wet and dry tensile strength,abrasion resistance, color stability, stability to heat, light,detergent, and solvents, flexibility, elongation, shape retention,and/or acceptable "hand." They are also particularly useful inmanufacturing methods which require relatively short cure time (rapidbonding rate), relatively high polymer-to-fiber cohesion, temperaturestability (during curing and subsequent treatment), and/or the use ofslightly acidic, neutral or alkaline application solutions ordispersions.

The extended polymer compositions can also be employed to bind two ormore substrates to each other or to coat such substrates and, thus, canbe employed as coatings and adhesives for forming laminates or othercomposite articles and for assembling adhesive-bound structures.Illustrative of such uses are binding or formation of laminates ofsubstrates such as acrylates, terephthalates, cellulosics (e.g., wood,paper, etc.), phenolic resins, urethane, metals, and the like; adheringcarpet backing to tufted or woven carpets, bonding vapor barriers(plastic films) to insulation, wall board, etc., adhering tiles or otherwall or floor coverings to concrete, wallboard, wood or other structuralmaterials, application of wood veneers to wood or composite backings,and numerous other similar adhesive applications.

When the extended polymer compositions are used as coatings for any oneof a variety of substrates, such as those identified immediately above,they may also contain one or more other ingredients, if desired, so longas such ingredients do not prevent hardening, or the compositions can beemployed simply as clear coatings. Illustrative, optional ingredientsinclude colorants, such as dyes and pigments, heat and ultra-violetstabilizers for the copolymers, accelerators for hardening the polymers,plasticizers, etc. Films and coatings may then be deposited with eitherthe emulsion or solution polymers, for example, by Weir coating, i.e.application of the polymer composition from a bath thereof having acontrolled overflow, or by brush, spray or doctor- or air-knife coating,by dip coating, etc., and the products may then be cured at ambient orelevated temperatures. Polymer concentrations suitable for use inlatexes and solutions employed for coatings and adhesives are similar tothose described hereinabove for textile binders. However, most bindingapplications, other than textile binding, and coating applications, suchas clear coatings and paints, will generally involve polymerconcentrations of at least about 5, typically at least about 10 weightpercent of the total composition. Thus, polymer concentrations useful insuch applications will generally be within the range of about 5 to about70, preferably about 10 to about 50 weight percent. The relativeproportions of polymer and chalcogenide useful in such coating andbinding applications are as described hereinabove.

The invention is further described by the following examples which areillustrative of specific modes of practicing the invention and are notintended as limiting the scope of the invention as defined by theappended claims.

EXAMPLE 1

A latex containing a copolymer having about 35.5 weight percent methylacrylate, 63.5 weight percent ethyl acrylate, and 1 weight percentitaconic acid was prepared as follows:

A monomer-surfactant preemulsion was prepared by combining 131.6 g.deionized water, 6.4 g. itaconic acid, 11.2 g. polyethoxylated nonylphenol surfactant having 50 moles ethylene oxide per mole, 11.2 g.polyethoxylated nonyl phenol surfactant having 40 moles ethylene oxideper mole, 13.6 g. polyethoxylated nonyl having 9 moles ethylene oxideper mole, 216.1 g. methyl acrylate, and 386.8 g. ethyl acrylate. Thereactor was initially charged with about 300 g. deionized water and 30ml. of the above-defined monomer-surfactant preemulsion, after which theresulting mixture was purged with nitrogen. This mixture was next heatedto about 52° C., and 0.6 g. potassium peroxydisulfate and 0.6 g. sodiummetabisulfite were added, with mixing. This mixture then was heated toabout 61° C. to initiate polymerization. At this point, the remainder ofthe monomer-surfactant preemulsion, along with 35 ml. of a solution of2.4 g. potassium peroxydisulfate in 100 ml. deionized water, and 35 ml.of a solution of 2.4 g. sodium metabisulfite in 100 ml. deionized waterwere gradually metered into the agitated reactor over a period of about4 hours. During this addition, the reaction medium was kept at aconstant temperature of about 61° C. and, at the completion of suchaddition, the latex had a polymer solids content of about 56 weightpercent, a viscosity, at 21° C., of 62 centipoise, and a pH of about5.3. Completion of the reaction was assured by post addition of about0.12 g. potassium peroxydisulfate and about 0.2 g. sodium metabisulfite.

EXAMPLE 2

Chromatographic grade filter paper was saturated with the copolymerlatex of Example 1 and oven dried at 150° C. for 3 minutes to form animpregnated paper sample containing about 23 weight percent polymer. A1-inch by 4-inch section of this sample was tested for wet tensilestrength (after dipping it in a 1% "Aerosol OT" solution, manufacturedby American Cyanamid Co., for about 4 seconds) on an Instron Model 1122tensile testing machine. A wet tensile strength of 1.8 pounds wasobtained. A similar sized polymer-saturated paper sample, after beingdipped for 4 seconds in neat perchlorethylene, had a "PCE" tensilestrength of 3.2 pounds.

EXAMPLE 3

A polymer emulsion was prepared using the compositions and procedures ofExample 1 with the exception that sufficient acetoacetoxyethylmethacrylate was added to the monomer-surfactant preemulsion to obtain afinished polymer containing about 4 weight percent of that monomer. Theconcentrations of the other monomers were reduced to 1 weight percentitaconic acid, 34 weight percent methyl acrylate and 61 weight percentethyl acrylate. The resulting latex had a solids content of 54 weightpercent, a pH of 5.4, and a viscosity of 24 centipoise. The wet and PCEtensile strengths, obtained as described in Example 2 with a polymerloading of 21.6 weight percent, were 5.0 and 7.4 pounds, respectively.

EXAMPLE 4

The latexes of Examples 1 and 3 were each diluted with deionized waterto about 25 weight percent solids concentration along with sufficientamounts of a 25 weight percent solution of urea to prepare the followinglatex compositions (% urea/% polymer): 0/25, 2.5/22.5, 3.8/21.2, 5/20,6.5/18.5, and 12.5/12.5. Using the procedure of Example 2 with an 18percent add on, the following wet tensile strength results wereobtained:

    ______________________________________                                        Wet Tensile Strength (Pounds)                                                 at Urea/Polymer Percents                                                      Latex  0/25   2.5/22.5 3.8/21.2                                                                             5/20 6.5/18.5                                                                             12.5/12.5                           ______________________________________                                        Ex. 1  1.1    0.8      0.7    0.6  0.45   0.4                                 Ex. 3  5.0    5.1      5.1    5.0  4.5    2.2                                 ______________________________________                                    

These results demonstrate that the polymer of Example 3 can be extendedwith a chalcogenide to form an extended polymer composition inaccordance with this invention with little or no loss of wet tensilestrength even when the amount of chalcogenide exceeds 1/3 the weight oftotal polymer. And even with a 50/50 chalcogenide/polymer composition,the polymer composition of Example 3, extended with the chalcogenide,had a significantly higher wet tensile strength (2.2) than did thepolymer of Example 1 (0.4).

EXAMPLE 5

The procedure of Example 2 was repeated with paper strips dipped inaqueous solutions containing 0, 2.5, 3.8, 5, 6.5, and 12.5 weightpercent urea. In each case, the observed tensile strength was 0.3 pound,i.e. there was no effect.

EXAMPLE 6

The procedure of Example 2 was repeated with paper treated with thelatex of Example 3, but without the addition of urea solution, with thefollowing results:

    ______________________________________                                        Polymer     25     22.5    21.2 20    18.5 12.5                               concentration, %                                                              Wet Tensile, lbs.                                                                         5.0    4.3     3.8  3.4   2.5  2.1                                ______________________________________                                    

Comparison of Examples 4 and 6 illustrates the effectiveness of theextended polymer compositions in contrast to compositions of comparablepolymer content in the absence of chalcogenide. In Example 4, there wasessentially no difference in cure sample tensile strength when 30percent of the polymer had been replaced by chalcogenide. In contrast,Example 6 illustrates that a 30 percent reduction of polymer content, inthe absence of added chalcogenide, resulted in a loss of approximatelyhalf the tensile strength of the textile binder.

EXAMPLE 7

An acrylic latex containing a copolymer having about 31.8 weight percentethyl acrylate, 59.7 weight percent butyl acrylate, 5 weight percentacrylonitrile, 1 weight percent itaconic acid, 0.5 weight percentacrylamide, and 2.0 weight percent acetoacetoxyethyl methacrylate wasprepared as follows:

A monomer-surfactant preemulsion was prepared by combining 14.37 litersdeionized water, 9.3 kg. ethyl acrylate, 17.425 kg. butyl acrylate, 1.47kg. acrylonitrile, 570 g. acetoacetoxyethyl methacrylate, 292 g.itaconic acid, 150 g. acrylamide, and 725 g. alpha-olefinic sulfonatesurfactant. The reactor was initially charged with 14 liters water,heated to 65° C., and purged with nitrogen, after which the describedpreemulsion, a catalyst solution comprised of 86 g. sodium persulfateand 21 g. sodium bicarbonate in 2.14 liters water, and an activatorsolution comprised of 53 g. erythorbic acid in 2.2 liters water wereadded over a three hour period. After the above solutions had beenadded, the reactor temperature was raised to 71° C. and the reaction wascontinued for an additional two hours, during which time small additionsof a mixture of t-butyl hyperoxide and erythorbic acid were made. Theresulting latex, after filtering, had a solids content of about 45weight percent, a pH of 2.8, and a viscosity of 50 centipoise.

EXAMPLE 8

The latex of Example 7 was evaluated using the procedures of Examples 2and 4, with a number of different extenders, and the results aresummarized in the following table:

    ______________________________________                                        Wet Tensile Strength (Pounds)                                                 at Extender/Polymer Percents                                                  Chalco-                                                                       genide  0/25    2.5/22.5  5/20  6.5/18.5                                                                             12.5/12.5                              ______________________________________                                        Urea    5.2     5.2       5.0   4.7    3.9                                    Thiourea                                                                              5.2     5.7       5.8   5.6    5.1                                    Dimethyl-                                                                             5.2     5.1       4.6   4.1    3.7                                    thiourea                                                                      Formamide                                                                             5.2     5.2       5.0   5.0    4.0                                    Methyl  5.2     5.7       6.1   5.4    5.0                                    formamide                                                                     Dimethyl                                                                              5.2     5.3       5.6   5.3    5.2                                    formamide                                                                     ______________________________________                                    

These results demonstrate that significant amounts, i.e., up to 50percent and more, of a variety of chalcogenide extenders can be used assubstitutes for polymer content in the latex without unacceptable lossof physical properties.

EXAMPLE 9

The latex of Example 7 was evaluated using the procedure of Example 8with neat perchloroethylene being used in place of an aqueous surfactantsolution. The results are summarized in the following table:

    ______________________________________                                        Perchloroethylene Tensile Strength (Pounds)                                   At Extender/Polymer Percents                                                  Chalco-                                                                       genide  0/25    2.5/22.5  5/20  6.5/18.5                                                                             12.5/12.5                              ______________________________________                                        Urea    6.4     5.3       4.4   3.5    2.0                                    Thiourea                                                                              6.4     6.0       6.0   6.1    4.2                                    Methyl  6.4     6.2       6.0   5.9    5.9                                    formamide                                                                     Dimethyl                                                                              6.4     6.2       6.3   6.3    6.2                                    formamide                                                                     ______________________________________                                    

These results demonstrate that the cohesive and adhesive strengths ofthe polymer can be maintained even when significant amounts ofchalcogenide extenders are substituted for corresponding amounts ofpolymer even after treatment with perchloroethylene.

EXAMPLE 10

The latex described in Example 8 containing 5 weight partsdimethylthiourea and 20 weight parts of the polymer can be applied byspraying onto one surface of a Mylar film and allowed to dry (cure) tocreate a clear coating on the Mylar film.

EXAMPLE 11

An extended polymer latex containing 13 weight parts methylformamide and37 weight parts of the polymer described in Example 7 can be prepared asdescribed in Example 8 to produce a composition having a total solidscontent of 50 weight percent. That composition can be applied to onesurface of a 1/16-inch thick wood veneer, by brushing the latex onto theveneer surface, and the coated veneer can be adhered to wallboard beforethe latex-coated surface is dried.

EXAMPLE 12

A pigmented, paint composition can be prepared by using, as a startinglatex, the dimethylformamide-containing latex prepared as described inExamples 7 and 8 by using undiluted dimethyl formamide and latexsolutions to prepare a composition containing 10 weight partsdimethylformamide, 40 weight parts polymer, and added pigment by theprocedures described in U.S. Pat. No. 4,421,889, the disclosure of whichis incorporated herein its entirety. The resultant composition can beemployed to apply a pigmented coating to prepared wooden surfaces.

While particular embodiments of the invention have been described, itwill be understood, of course, that the invention is not limited tothese embodiments, since many obvious modifications can be made, and itis intended to include within this invention any such modifications aswill fall within the scope of the appended claims.

What is claimed is:
 1. A substrate having coated on at least a portionof one surface thereof a composition comprising (A) a polymer havingpendant functional groups attached to the polymer backbone having theformula: ##STR12## wherein R₁ is a divalent organic radical at leastthree atoms in length, X is --CO--R₄ or --CH and R₄ is hydrogen or amonovalent organic radical, and (B) a chalcogenide selected from thegroup consisting of urea, thiourea, biuret, triuret, and combinationthereof.
 2. The coated substrate defined in claim 1, wherein saidpolymer is selected from(1) conjugated diolefin polymers containing atleast 30 weight percent of one or more conjugated diene monomers having4 to 8 carbon atoms and 0 to about 70 weight percent of one or morealkenyl-substituted monoaromatic monomers, (2) olefin-esterinterpolymers containing at least about 1 weight percent of a monoolefinmonomer having up to 4 carbon atoms and at least 40 weight percent of analkenyl or alkenol ester of a saturated carboxylic acid, (3)olefinically unsaturated carboxylic acid ester polymers containingpolymerized, olefinically unsaturated monomers of which at least 40weight percent are polymerized olefinically unsaturated carboxylic acidester monomers, (4) polymers of olefinically unsaturated monomerscontaining at least 30 weight percent alkenyl ether monomer units, (5)polymers of vinylidene chloride or vinyl chloride with or without otherpolymerized, olefinically unsaturated monomers, and (6) combinationsthereof,and said composition comprises at least about 5 weight percentof said chalcogenide based on the weight of chalcogenide plus drypolymer.
 3. The coated substance defined in claim 2, wherein saidpolymer comprises a member selected from the group consisting ofpolymerized acrylic acid, itaconic acid, acrylamide, acrylonitrile,hydroxyethylacrylate, and combinations thereof.
 4. The coated substancedefined in claim 2, wherein said polymer comprises one or more of saidolefinically unsaturated carboxylic acid ester polymers.
 5. The coatedsubstance as defined in claim 2, wherein R₁ is a divalent organicradical having up to about 40 carbon atoms, R₄ is hydrogen or amonovalent organic radical having up to about 10 carbon atoms, R₁ andR₄, when they are organic radicals, comprise organic radicals containinghydrogen and carbon with or without heteroatoms selected from the groupconsisting of oxygen, phosphorus, sulfur, nitrogen, and combinationsthereof, and which can be substituted or unsubstituted with substituentsselected from the groups consisting of hydroxy, halo, thio, thiol, andamino substituents, and combinations thereof.
 6. The coated substratedefined in claim 1, wherein R₁ is a divalent organic radical having upto about 40 carbon atoms, R₄ is hydrogen or alkyl having up to about 10carbon atoms, and said chalcogenide constitutes at least about 10 weightpercent of said composition based on the combined weight of said polymerand said chalcogenide.
 7. The coated substrate defined in claim 6,wherein R₁ has the formula ##STR13## wherein Y and Z are independentlyselected from oxygen and sulfur, and R₃ is selected from substituted andunsubstituted alkylene, alkylene-oxy, alkyleneimine and alkylene-thioradicals.
 8. The coated substrate defined in claim 1, wherein saidpolymer comprises about 0.1 to about 30 weight percent of saidfunctional monomer.
 9. The coated substrate defined in claim 1, whereinsaid composition is free of polyvalent metals, compounds and complexes.10. The coated substrate defined in claim 1, wherein said polymer isfree of crosslinking agents.
 11. The coated substrate defined in claim1, wherein X is --CO--R₄, and R₄ is selected from hydrogen andhydrocarbyl radicals having up to about 10 carbon atoms.
 12. The coatedsubstrate defined in claim 1, wherein X is --CO--R₄, R₁ is selected fromcyclic and acrylic divalent organic radicals 3 to about 40 atoms inlength, R₄ is selected from hydrogen and monovalent organic radicalshaving up to 10 atoms other than hydrogen, and said chalcogenideconstitutes at least about 10 weight percent of said composition basedon the combined weight of said polymer and said chalcogenide.
 13. Thecoated substrate defined in claim 1, wherein said polymer comprises atleast about 0.1 weight percent of a polymerized functional monomerhaving the formula ##STR14## wherein R₄, R₅ and R₆ are independentlyselected from hydrogen and monovalent organic radicals, Y and Z areindependently selected from oxygen, sulfur and NR₇, R₇ is hydrogen or amonovalent hydrocarbyl radical having up to about 6 carbon atoms, and R₃is a divalent hydrocarbyl radical up to 40 atoms in length, which maycontain heteroatoms selected from oxygen, phosphorus, sulfur andnitrogen.
 14. The coated substrate defined in claim 13, wherein R₄, R₅and R₆ are selected from hydrogen and, hydroxy, halo, thiol andamino-substituted monovalent hydrocarbyl radicals having up to 10 carbonatoms, R₇ is selected from hydrogen and monovalent hydrocarbyl radicalshaving up to 10 atoms other than hydrogen, and Y and Z are independentlyselected from oxygen and sulfur.
 15. The coated substrate defined inclaim 1, wherein said polymer is selected from said olefinicallyunsaturated carboxylic acid ester polymers and comprises at least about0.1 weight percent of a polymerized functional monomer selected from thegroup consisting of acetoacetoxyethyl-methacrylate andacetoacetoxyethylacrylate, and combinations thereof.
 16. The coatedsubstrate defined in claim 1, wherein R₁ has the formula ##STR15##wherein Y and Z are independently selected from oxygen, sulfur and NR₇,R₃ is a divalent organic radical up to about 40 atoms in length, and R₇is H or hydrocarbyl having up to about 6 carbon atoms.
 17. The coatedsubstrate defined in claim 16, wherein R₃ is selected from substitutedand unsubstituted alkylene, alkylene-oxy, alkyleneimine andalkylene-thio radicals, Y and Z are oxygen, X is --CO--R₄, and R₄ isselected from hydrogen and hydrocarbyl having up to about 10 carbonatoms.
 18. The coated substrate defined in claim 1, wherein said polymercomprises a polymerized, olefinically unsaturated carboxylic acidmonomer having up to about 10 carbon atoms.
 19. The coated substratedefined in claim 1, wherein said chalcogenide is water-soluble.
 20. Thecoated substrate defined in claim 1, wherein, in addition to saidpendant functional groups, said polymer consists essentially of (A) atleast about 10 weight percent polymerized ester monomers selected fromthe group consisting of acrylic acid and methyacrylic acid esters ofhydroxy-substituted and unsubstituted alcohols in which the alcoholmoiety has up to about 10 carbon atoms, and combinations thereof, in thepresence or absence of (B) polymerized monomers selected from the groupconsisting of vinyl esters of carboxylic acids, the acid moiety of whichcontains from 1 to about 20 carbon atoms, ethylene, propylene, stryene,vinyl toluene, vinyl halides, olefinically unsaturated nitriles,olefinically unsaturated carboxylic acids having up to about 10 carbonatoms, and combinations thereof.
 21. The coated substrate defined inclaim 20, wherein X is --CO--R₄.
 22. The coated substrate defined inclaim 21, comprising at least about 10 weight percent of saidchalcogenide based on the combined weight of said polymer andchalcogenide.
 23. A substrate having coated on at least a portion of onesurface thereof a composition comprising; (I) a polymer having pendantfunctional groups attached to the polymer backbone having the formula:##STR16## wherein R₁ is a divalent organic radical at least three atomsin length, X is --CO--R₄ or --CH, and R₄ is hydrogen or a monovalentorganic radical, wherein in addition to said pendant functional groups,said polymer consists essentially of (A) at least about 10 weightpercent polymerized ester monomers selected from the group consisting ofacrylic and methyacrylic acid esters of hydroxy-substituted andunsubstituted alcohols, in which the alcohol moiety has up to about 10carbon atoms, and combinations thereof, in the presence or absence of(B) polymerized monomers selected from the group consisting of vinylesters of carboxylic acids, the acid moiety of which contains from 1 toabout 20 carbon atoms, ethylene, propylene, styrene, vinyl toluene,vinyl halides, olefinically unsaturated nitriles, olefinicallyunsaturated carboxylic acids having up to about 10 carbon atoms, andcombinations thereof; and (II) a chalcogenide selected from the groupconsisting of urea, thiourea, biuret, triuret, and combination thereof,wherein the chalcogenide is contained in the composition at a level ofat least about 10 weight percent, based on the combined weight ofpolymer and the chalcogenide.
 24. The coated substrate defined in claim23, wherein X is --CO--R₄.
 25. A substrate coated on at least a portionof one surface thereof with a composition comprising (A) a polymerformed by copolymerizing a functional monomer having the formula##STR17## wherein R₄, R₅, and R₆ are independently selected fromhydrogen and monovalent organic radicals, Y and Z are independentlyselected from oxygen, sulfur, and NR₇, R₇ is hydrogen or a monovalenthydrocarbyl radical having up to about 6 carbon atoms, and R₃ is adivalent hydrocarbyl radical up to 40 atoms in length, which may containheteroatoms selected from oxygen, phosphorus, sulfur, and nitrogen, withother comonomers, said copolymerization being conducted in the presenceof (B) a chalcogenide selected from the group consisting of urea,thiourea, biuret, triuret, and combination thereof.
 26. The coatedsubstrate defined in claim 25, wherein said copolymer is formed byemulsion copolymerization of said monomers in aqueous medium, and saidchalcogenide is water soluble.
 27. The coated substrate defined in claim26, wherein said polymer is selected from(1) conjugated diolefinpolymers containing at least 30 weight percent of one or more conjugateddiene monomers having 4 to 8 carbon atoms and 0 to about 70 weightpercent of one or more alkenyl-substituted monoaromatic monomers, (2)olefin-ester interpolymers containing at least about 1 weight percent ofa monoolefin monomer having up to 4 carbon atoms and at least 40 weightpercent of an alkenyl or alkenol ester of a saturated carboxylic acid,(3) olefinically unsaturated carboxylic acid ester polymers containingpolymerized, olefinically unsaturated monomers of which at least 40weight percent are polymerized olefinically unsaturated carboxylic acidester monomers, (4) polymers of olefinically unsaturated monomerscontaining at least 30 weight percent alkenyl ether monomer units, (5)polymers of vinylidene chloride or vinyl chloride with or without otherpolymerized, olefinically unsaturated monomers, and (6) combinationsthereof,and said composition comprises at least about 5 weight percentof said chalcogenide based on the weight of chalcogenide plus drypolymer.
 28. The coated substrate defined in claim 27, wherein saidpolymer further comprises a member selected from the group consisting ofpolymerized acrylic acid, itaconic acid, acrylamide, acrylonitrile,hydroxyethylacrylate, and combinations thereof.
 29. The coated substratedefined in claim 27, wherein said polymer comprises one or more of saidolefinically carboxylic acid ester polymers.
 30. The coated substratedefined in claim 26, wherein said polymer comprises about 0.1 to about30 weight percent of said functional monomer.
 31. The coated substratedefined in claim 26, wherein said composition is free of polyvalentmetals, compounds and complexes.
 32. The coated substrate defined inclaim 26, wherein said polymer is free of crosslinking agents.
 33. Thecoated substrate defined in claim 26, wherein R₄, R₅ and R₆ are selectedfrom hydrogen and, hydroxy, halo, thiol and amino-unsubstitutedmonovalent hydrocarbyl radicals having up to 10 carbon atoms, R₇ isselected from hydrogen and monovalent hydrocarbyl radicals having up to10 atoms other than hydrogen, and Y and Z are independently selectedfrom oxygen and sulfur.
 34. The coated substrate defined in claim 26,wherein said polymer is selected from said olefinically unsaturatedcarboxylic acid ester polymers and comprises at least about 0.1 weightpercent of a polymerized functional monomer selected from the groupconsisting of acetoacetoxyethyl-methacrylate andacetoacetoxyethylacrylate, and combinations thereof.
 35. The coatedsubstrate defined in claim 26, wherein said polymer comprises apolymerized, olefinically unsaturated carboxylic acid monomer having upto about 10 carbon atoms.
 36. The coated substrate defined in claim 26,comprising at least about 10 weight percent of said chalcogenide basedon the combined weight of said chalcogenide and said polymer.
 37. Thecoated substrate defined in claim 26, wherein, in addition to saidpendant functional groups, said polymer consists essentially of (A) atleast about 10 weight percent polymerized ester monomers selected fromthe group consisting of acrylic and methyacrylic acid esters ofhydroxy-substituted and unsubstituted alcohols, in which the alcoholmoiety has up to about 10 carbon atoms, and combinations thereof, in thepresence or absence of (B) polymerized monomers selected from the groupconsisting of vinyl esters of carboxylic acids, the acid moiety of whichcontains from 1 to about 20 carbon atoms, ethylene, propylene, styrene,vinyl toluene, vinyl halides, olefinically unsaturated nitriles,olefinically unsaturated carboxylic acids having up to about 10 carbonatoms, and combinations thereof.
 38. The coated substrate defined inclaim 15, wherein said polymer comprises one or more of saidolefinically unsaturated, carboxylic acid ester polymers.
 39. The coatedsubstrate defined in claim 25, wherein said functional monomer comprisesa member selected from the group consisting ofacetoacetoxyethylmethacrylate and acetoacetoxyethylacrylate, andcombinations thereof.